Zirconium anti-soil treatment of synthetic fibers and resultant article

ABSTRACT

DURABLE ANTI-SOILING CHARACTERISTICS ARE IMPARTED TO TEXTILE ARTICLES COMPRISED OF SYNTHETIC FIBERS BY TREATING THEM WITH AN ACIDIC AQUEOUS SOLUTION CONTAINING A ZIRCONIUM SALT AND A DERIVATIVE OF AMMONIA, THEN DRYING THE TEXTILE ARTICLE THEREBY TO BOND THE EVAPORATION RESIDUE OF THE SOLUTION, A ZIRCONIUM REACTION PRODUCT, TO THE SYNTHETIC FIBERS. THE PROCESS MAY BE VARIED BY FIRST TREATING THE FIBERS WITH THE ZIRCONIUM SALT FOLLOWED BY TREATMENT WITH THE DERIVATIVE OF AMMONIA.

United States Patent f 3,671,292 ZIRCONIUM ANTI-SOIL TREATMENT OF SYN- THETIC FIBERS AND RESULTANT ARTICLE Julian J. Hirshfeld and Bertie J. Reuben, Decatur, Ala.,

assiguors to Monsanto Company, St. Louis, M0.

N0 Drawing. Continuation-impart of application Ser. No. 564,003, July 11, 1966, which is a continuation-in-part of applications Ser. No. 419,549, Dec. 18, 1964, and Ser. No. 419,601, Dec. 18, 1964. Thisapplication July 15, 1969, Ser. No. 841,977

Int. Cl. D06m 11/04, 13/00 U.S. Cl. 117-62 17 Claims ABSTRACT OF THE DISCLOSURE Durable anti-soiling characteristics are imparted to textile articles comprised of synthetic fibers by treating them with an acidic aqueous solution containing a zirconium salt and a derivative of ammonia, then drying the textile article thereby to bond the evaporation residue of the solution, a zirconium reaction product, to the synthetic fibers. The process may be varied by first treating the fibers with the zirconium salt followed by treatment with the derivative of ammonia.

BACKGROUND OF THE INVENTION This invention relates to a process of treating textile articles to impart anti-soiling characteristics thereto and to textile articles treated by such a process. More specifically, the invention concerns a process of treating textile articles comprised of synthetic fibers with zirconium salts to impart anti-soiling characteristics thereto and to such articles treated by the process.

In the textile field and particularly in the carpet industry, where in recent years pastel colors and the use of carpets next to entrance ways have become popular, a need for anti-soiling characteristics built into textile articles has become more demanding. Also, the increased use of hydrophobic fibers, such as nylon, polyester, and acrylic, in textile articles has increased the need for anti-soiling properties .since these fibers tend to accumulate static charges of electricity and, as a result, attract soiling particles.

Soiling of textile articles is generally effected by three methods, i.e., directly contacting the article with soiling particles, contacting the article with air-borne soiling particles, and contacting the article with liquid-borne substances containing soiling particles. Retention of these soiling particles on the textile article can be explained by three mechanisms, i.e., purely mechanical forces of entrapment or occlusion, interfacial adhesional forces such as Van der Walls forces and electrostatic forces. Removal of the soiling particles from the textile article is dependent on 3,671,292 Patented June 20, 1972 Ice numerous factors. Generaly speaking, large soiling particles can be readily removed whereas soiling particles within the range of less than 20 microns, and especially around 1 micron, are extremely difficult to remove from the textile article.

The textile industry has tried to prevent the soiling of textile articles by treating the articles with numerous organic and inorganic compositions. Most of these compositions are merely deposited on the article without any chemical bonding, and, as a result, are not efiective over a prolonged period of time and are easily removed by washing, dry-cleaning or even vacuuming. For example, articles having interstices on the surface of the fiber are made soil-resistant by depositing small particles, usually less than 20 microns in diameter, of silicas on the fiber to fill the interstices and thus prevent the entrapment of soiling particles therein. However, most of these silicas do not chemically bond to the fiber and are easily removed by washing and vacuuming and, in some cases, cause dusting problems. Also, the textile industry has tried to prevent the build-up of static charges on hydrophobic fibers by treating these fibers with cationic softeners; however, limited success has been experienced since most of these softeners are usually water soluble and are readily removed by washing.

It is anobject of this invention to provide a process for imparting anti-soiling characteristics to textile articles comprised of synthetic fibers.

Another object of this invention is to provide textile articles comprised of a synthetic fiber selected from the group consisting of polyamide fiber, polyester fiber, acrylic fiber, olefin fiber, modacrylic fiber, and spandex fiber with a process which imparts good anti-soiling characteristics thereto.

Other objects of the invention will become apparent as the invention is fully developed within the specification.

These and other objects of this invention are accomplished by providing a process of treating a textile article comprised of synthetic fibers comprising contacting the article with an acidic aqueous solution containing a zirconium salt and a nitrogen containing base, then drying the textile article, thereby to bond the evaporation residue of the solution, a zirconium reaction product, to the synthetic fibers.

The term textile article is meant to include fiber, yarn, all types of fabric, all types of carpets, and any textile article comprised of synthetic fiber. The term synthetic fiber is meant to include spandex fiber (a manufactured fiber in which the fiber-forming substance is any longchain synthetic polymer composed of at least by weight of a segmented polyurethane) polyester fiber (a manufactured fiber in which the fiber-forming substance is any long-chain synthetic polymer composed of at least 85 by weight of an ester of a dihydric alcohol and a dibasic acid or derivative thereof, such as terephthalic acid, or dimethylterephthalate), olefin fiber (a manufactured fiber in which the fiber-forming substance is any long-chain synthetic polymer composed of at least 85% by weight of ethylene, propylene, or other olefin units), modacrylic (a manufactured fiber in which the fiber-forming substance is any long-chain synthetic polymer composed of less than 85 but at least 35% by weight of acrylonitrile units), nylon fiber .(a manufactured fiber in which the fiber-forming substance is any long-chain synthetic polyamide having recurring amide groups (CO-NH--) as an integral part of the polymer chain), and acrylic fiber (a manufactured fiber in which the fiberforming substance is any long-chain synthetic polymer composed of at least 85% by weight of acrylonitrile units). The textile article may contain minor amounts of material or fiber other than the synthetic fiber, e.g., jute backing in a carpet, etc.

The zirconium salts useful in the invention include any zirconium salt that is water soluble in the sense that they can be made soluble in water at certain pHs. Zirconium salts usually contain small amounts of hafnium, generally from about 0.5% to about 4.5% by weight. Hafnium is extremely similar to zirconium and, for purposes of this invention, it is to be assumed that where zirconium salts are mentioned herein it is meant to include zirconium salts with small concentrations, i.e., less than about 5.4% of hafnium. Examples of useful zirconium salts include zirconium acetate, zirconium oxychloride, zirconium sulfate, zirconium acetylacetonate, potassium zirconyl carbonate, zirconium chloride, zirconium fluoride, zirconium nitrite, ammonium zirconyl carbonate, sodium zirconium oxychloride, sodium zirconium glycolate, and zirconium tetrachloride. From an economical standpoint, zirconium acetate is a particularly useful zironium salt.

A nitrogen containing base is present in the acidic aqueous solution containing the zirconium salt. The nitrogen containing base can be either an organic or an inorganic derivative of ammonia. The organic nitrogen containing base can be a primary amine, a secondary amine, a tertiary amine, or a quaternary ammonium salt and can contain one or more groupings selected from the class consisting of alkyl, aryl, alkaryl and aralkyl. The groupings can contain substituents such as hydroxyl, carboxyl, sulfonic, nitro and halogens (chloro, bromo, fluoro, and iodo). Examples of useful inorganic nitrogen containing bases include hydroxylamine sulfate, hydroxylamine chloride, sulfamic acid, ammonium sulfamate, hydrazine, hydroxylamine, ammonia, and ammonium carbonate. Examples of useful organic nitrogen containing bases include ammonium carbamate, ethylene diamine, 1,6-hexamethylenediamine, guanidine, pyridine, monoethanolamine, glycine, aminoacetic acid, p-aminobenzoic acid, aniline, aniline hydrochloride, furfurylamine, o-toluidine, morpholine, N-methylfurfurylamine, N-methyltetrahydrofurfurylamine, and piperazine. The purpose of the nitrogen containing base is not completely explainable; however, it is known that the nitrogen containing base does help the deposition of the zirconium residue onto the fiber. In regards to fibers containing nitrogenous sites therein, it may be explained however, the explanation is not to be considered as a limitation hereof, that the nitrogen containing base forms a loose complex with the zirconium salt and this complex, due to its changed electrical bharacteristic, enables the zirconium salt to more readily attach itself to the nitrogenous sites in the fiber. More simply explained, the nitrogen containing base acts as a transfer agent or carrier for the zirconium compound. Its use results in a more durable deposition of the zirconium residue on the synthetic fibers than would otherwine be accomplished. The acidity of the aqueous solution should be within a pH range of from about 1.5 to less than about 7. Acids such as sulfuric acid, hydrochloride acid, acetic acid, phosphoric acid and formic acid are examples of acids useful to adjust the pH of the solution. Preferably, it is desired that the pH of the solution be within the range of from about 2 to about 5. The acidity of the aqueous solution helps to solubilize the zirconium salt and the nitrogen containing base, and to maintain the zirconium in solution until, when the article is dried, a zirconium residue is thereby uniformly-de posited in the form of a microscopic cohesive and adhesive substantially continuous film of particles imbedded within the surface of the fibers. The zirconium salt should be present in the acidic aqueous solution in amounts ranging from about 0.2% to about 20.0%, and preferably within the range of from about 1% to about 5%, the percents "based on' the weight of the textile article. Useful weight ratios of the zirconium salt to the nitrogen containing base within the acidic aqueous solution are from about 5:0.2 to about 1:1, and preferably about 5:3, respectively.

The temperature of the acidic aqueous solution should be within the range of from about room temperature to about 212 F. Higher temperatures, for example within the range of from about 175 F. to about the boiling point temperature of the solution are preferred in facilitating the contacting of the textile article with the acidic aqueous solution.

Contacting the textile article with the acidic aqueous solution can be accomplished by immersion, padding, spraying, exhaust bath, roll application and any other like means known in. the textile art. The method of contacting should be adequate to completely wet the textile article with the solution-Contact time can vary from a few seconds to minutes or even hours. For example, where the acidic aqueous solution is padded on the textile article, the contact time can vary from about a half of a second to about 3 seconds; where an exhaust procedure is used, the contact time can vary from about 15 minutes to about 30 or more minutes; and where the article is immersed in the solution, the contact time can vary from about 5 minutes to about minutes. Contact time should be measured from the time of contact of the solution described. If, for example, it should be desirable to introduce the nitrogen-containing base while the textile article is in contact with the acidic aqueous solution of the zirconium salt, contact time would be measured from the time of introduction of the nitrogen-containing base.

.After the textile article is contacted with the acidic aqueous solution, the article is dried. Drying can be effected at temperatures within the range of from about room temperature up to about 350 F. Preferably, the textile articles are dried at temperatures within the range of 200 F. to 350 F.

Textile articles treated by the process of this invention exhibit good anti-soiling properties. Such properties are sufiiciently afiixed thereto to withstand dry-cleaning, washing, vacuuming, etc. Also, the textile article can be sub jected to a dyeing process either before or after it is treated with the acidic aqueous solution of this invention.

The exact nature or explanation of why the textile articles treated by the process of this invention exhibit good anti-soiling properties is not fully understood. It is known that the zirconium residue is adequately bonded to withstand washing, dry-cleaning, and vacuuming.

The following examples are presented to illustrate the anti-soiling properties of the treated textile articles. All the samples used in the following examples are initially cleaned by scouring for 30 minutes at F. in an aqueous solution (liquor to goods ratio being 40:1) containing 0.5% of a nonionic surfactant and 0.5 of tetrasodium pyrophosphate, percents based on weights of goods. After the samples are soiled, they are rinsed in cold water and dried at about 200 F. To show that the textile articles can be treated before being dyed, some of the samples are blank dyed. Such a blank dyeing procedure depends on the particular fiber. For example, where the fiber is a nylon fiber or an olefin fiber the sample is blank dyed by immersing it for 60 minutes in a boiling aqueous solution (liquor to goods ratio being about 35: 1) containing about 0.5 (based on weight of goods) of a nonionic surfactant followed by rinsing and drying. Other blank dyeing procedures for particular fibers are of common knowledge in the art.

To illustrate the anti-soiling properties imparted to the textile articles, photo reflectance measurements or readings are made of two samples (dimensions being 2" x 4") of the textile article used in each example. Initial reflectance readings are made after the textile article is first treated in accordance with the invention and then reflectance readings are made after the sample is soiled. The difference in the reflectance readings indicate the antisoiling properties or characteristics of the samples, i.e. a large number indicates poor anti-soiling properties whereas a small number indicated good anti-soiling properties. The photo reflectance readings are measured by using a Photovolt Reflectance Meter (Model No. 610, Photovolt Corp., New York City, N. Y.). The samples of the textile articles are soiled by either of two methods, i.e. by an artificial soiling test or by a floor soiling test. The artificial soiling test is accomplished by placing the samples in a one gallon wide mouth jar having therein two glass rods long by diameter) glued on opposite sides of the jar and containing (based on Weight of the sample) of artificial soil and 10 number two rubber stoppers. The artificial soil has the following composition (the soil is sifted through a 30 mesh screen):

Animal charcoal 6.6 Mineral oil 1.1

Total 100.0

The jar is then sealed, placed on a ball mill and rotated at 95-100 r.p.m. for 30 minutes in a clockwise direction and 30 minutes in a counter-clockwise direction at the same r.p.m. Thereafter, the samples are removed from the jar, vacuumized, and the photo reflectance readings of the two samples measured. The difference between the average initial reflectance readings and the average of the final reflectance readings indicate the degree of soil resistance. As mentioned earlier, a small photo reflectance difference number indicates a good anti-soiling property whereas a large number indicates a poor anti-soiling property of the textile article. The procedure in the floor soiling test is the same as the above artificial soiling test except the samples are soiled by placing them in the pathway of a well-traveled walkway and soiled by natural means, such as by shoes, air-borne soiling particles, etc. Control samples, that is samples that are not treated with the acidic aqueous solution containing the zirconium salt and the nitrogen containing base, are soiled under the same conditions as the test samples. The test results of the control samples as compared to the test results of the test samples indicate the significances of the invention. The percent increase in anti-soiling characteristic imparted to the samples is indicated in the examples as Percent Improvement of Test Sample Over Control Sample. The initial reflectance readingsof the control samples are taken after the control samples are scoured. Percents where used are based on weight unless otherwise specified.

Example 1 The following scoured samples are immersed in separate aqueous solutions (liquor to goods ratio 40:1) at room temperature, each solution has a pH of 2.4 and contains 1.1% zirconium acetate, 3% sulfuric acid and 3% hydroxylamine sulfate, the percents based on weight of ,the samples. The solutions are heated to and maintained at the boiling point for 30 minutes. Thereafter, the samples are removed from the solutions, rinsed in water, blank dyed, rinsed again in water, dried, and then subjected to the artificial soiling test. The results of the soiling test are indicated in Table 1., Control samples, i.e. samples identical to their respective test samples except that they are. not treated in the aqueous solutions, are .presentedftoshow. the significance of the invention.

TABLE I Percent improvement of Reflec- Difiertest Initial tance ence in sample refiecreading reflecover tance after tance control Sample reading soiling readings sample (a) Nylon 6.6 knit (Cumuloft, a trademark of Chemstrand Company):

Control 83 27 56 Test 83 39 a4 21 (b) Nylon 6.6 knit (501 Nylon, marketed by E. I. du Pont de N emours & Company):

gonttrol 28 52 es 80 40 40 2 (c) Nylon 6 3 gent 24 53 as A... 33 44 1 (d) Rayon knit: 7

gonttrol 66 25 42 es 66 30 36 14 (e) Acrylic knit (copolymer containing 93% acrylonitrile and 7% vinyl acetate):

Control 67 29 38 Test 68 38 30 21 (f) Acryhc yarn (Orlon type 33 Orlon a trademark of E. I. du Pont de N emours & 00.):

gonttrol 64 33 31 es 65 37 28 10 (g) Acrylic knit acrylonitrile, 7% vinyl acetate and 3% vinyl bromide):

Control 66 30 36 Test 66 40 26 28 (h) Spandex knit (Blue C,

a trademark of Chemstrand 00.):

Control 71 15 56 Test 72 17 55 l. 8 (1) Polypropylene knit:

Control 75 22 53 Test. 77 28 49 7. 5 (1) Acrylic yarn (76.5% being a copolymer of 93% acrylonitrile and 7% vinyl acetate, 10.5% being a copelymer of 50% acrylonitrile and 50% methylvinyl pyridine and 13% of polyvinyl chloride):

Control 63 38 25 Test 64 51 13 48 (k) Polyester knit (Blue C, a trademark of Chemstrand Company):

Control 82 28 54 Test s3 32 51 5.6

Example 2 I Samples are treated as described in Example 1 except the solutions are at a pH of 3.7 and contain 3% acetic acid instead of the sulfuric acid. The results of the artificial soiling test are indicated in Table II.

TABLE II Percent improve ment 0 f Refl'ec- Differ- Initial tance ence in sample refiecreading reflecover tance' after tance control Sample reading soiling readings sample (a) Nylon 6.6 knit (Cumuleft, a trademark of Chemstrand Company): Control 83 27 56 Test 83 37 46 18 (b) Nylon 6.6 knit (501 Nylon, marketed by E. I. du Pont de Nemours & Company): Control 80 28 52 Test 81 38 43 17 (0) Nylon 6 knit:

Control 77 24 53 Test 78 29 49 7. 5 (d) Rayon knit:

Control 66 24 42 Test 66 28 38 9. 5 (0) Acrylic knit (copolymer containing 93% acrylonitrile and 7% vinyl acetate): Control 67 29 38 Test 65 40 25 34 TABLE II-Continued Example 4 Perce11t Acrylic carpet samples composed of 76.5% of a co- 353; polymer being 93% acrylonitrile and 7% vinyl acetate, 11 1 Rfle- Diflertest 10.5% of a copolymer being 50% acrylonitrile and 50% 6111 SBJl'l 6 t 3 1 x-3:, g 5 methylvmylpyrld ne and 13% polyviuylchlorlde are tance lter tance co trol treated as described 1n Example 1 except that half of Sample madmg smlmg readmgs F the samples are dyed a gold shade and half are blank (r Acrylic k1 i; (90%1acry1- dyed. The samples are subjected to the floor soiling test,

oni rile,7 viny acetate 3% vinyl results of the test are indicated in Table IV. bromide)" Control 66 30 36 Test-- 61 36 25 at Acrylic (e) E93 I a t g TABLE IV 0 11 011 8 Nem'ours & 00.): inllgrgegt Control 6 33 31 15 ment of Test 64 4O 24 23 Reflcc- Difier- (h) Spandex kmt (Blue 0, Initial tance ence in sample a mark of Chemrefiecreading reflec- Over p y): 71 15 56 tance after tance control Test '.IIIIIIII.-;.IIIII 72 1s 54 as sample madmg swung "admgs Sample (a) Dyed gold shade:

Control 31 18 13 Test 31 21 10 2a (b) Blank dyed:

Control- 47 22 Test 55 as 17 23 Example 3 25 The following samples are treated as described in Example 1 except the aqueous solution is at a pH of l 5 2.6 and contains 5% zirconium oxychloride, 3% hydro- EXamP e chloric acid and 3% hydroxylamme hydrochloride. The A li k i Samples composed of 765% of a l results of the soiling test are indicated in Table III. mer being 93% acrylonitrile and 7% vinyl acetate 10.5% of a copolymer being 50% acrylonitrile and 50% methylvinylpyridine and 13% polyvinylchloride are treated as described in Example 1 except the aqueous solution is at a pH of 3.9 and contains 3% ammonium TABLE 111 sulfamate instead of the hydroxylamine sulfate. The re- Pment sults of the artificial soiling test are indicated in Table V. improvement of Reflec- Difiertest Initial tance ence in sample reflec reading refleeover TABLE V tance after tance control Sample reading soiling readings sample P nt improve- (a) Nylon 6.6 knit (Cumument of loft, a trademark of Reflec- Difier- Chemstrand Company): Initial tance ence in sample Control 83 27 56 retleereading reflecover Test 83 3 52 7. 1 tance after tance control (b) Nylon 6.6 knit (601 Sample reading soiling readings sample Nylon, marketed by E. I. du Pout de Nemours & (a) Control 53 23 30 Company): Test 56 30 26 13 Control r 80 28 52 Test 80 31 49 5.8 (0) Acrylic knit (copolymer containing 93% acrylonitrig and il% vinyl acetate): 67 29 38 i on re d Eesti, 67 a4 3a 13 Example 6 teig0$i1le0r93 Samples of acrylic knit are immersed -for 30 minutes aery in boiling aqueous solutions (liquor to goods ratio being vlnyl acetate, 10.5% being apopolymer 50% acme. 30.1), the soltu1ons contaimng compositions as outlined $12 l gg a ggg in Table VI. Thereafter the samples are removed from oifi fi chloride): 0 the baths, rinsed in water, blank dyed, rinsed again in gg 2 2 water, dried and then subjected to the artificial soiling test. The results of the test are indicated in Table VI.

TABLE VI Percent improvement OI Rcllcc- Dillertest 111-! Initial tance ence in sample of reflec reading reflecover solutance after tance control Sample Solution composition tion reading soiling reading sample (a) Control 58 37 21 Zirconium acetate, 0.66%; hydroxylamine sulfate, 1.0%; sulfuric acid, 0.24%. 1.9 63 51 12 43 Zirconium acetate, 1.1%; hydroxylamine sulfate, 3.0%; sulfuric acid, 0.4% 2. 9 66 6 71 (d) Te Zirconium acetate, 1.1%; hydroxylamine sulfate, 1.0%; sulfuric acid, 0.4% 2 9 67 57 10 52 Example 7 TABLE IX Scoured samples of acrylic knit are treated as de- Percent scribed in Example 1 except the aqueous solution conmpr e tains 1.1% zirconium acetate (percent based on weight Difl 1,3,

of sample), sulfuric acid to adjust the pH of the solution 5 v ferencgin sample to the below indicated pH numbers, and 3% (percent Nitrogen containing 3 5,55,, ggii based on we1ght of sample) of a mtrogen containing base p e e fl readmgs sa p e as indicated in Table VII. Results of the artificial soil- (8) Control 47 ing test are indicated as diflierence in reflectance read- 3 2 g; 3

ings and are outlined in the following table, Table VII. S 37 21 3.5 as 19 j 4.7 29 as Ethylene diamine 8.7 34 28 (h) Test 1,6-hexamethylenedi- 4.7 36 23 i as orp nine 5 TABLE VII I'Iest N-metlgyltgrurglzamipe.-- 4.; 28 13 est N-met y e ra y r0 ur- 4. 8 1

g f furylamine.

xgg (m) Test Piperazine 5.6 44 6.4 Diffep me t gt (11) Test Hexamethylene tetramine. 4.6 44 6.4 erencein smgle (0) Test P-aminobenzoic acid 4.2 34 28 N: t pHlof riflecctveii l rogen C011 almng S0 11- 211109 (301! 1'0 Sample base tion readings sample The test samples treated as described in Examples 1-9 (a) Coma 23 were subjected to repeated washing and vacuuming with- (b) Test" Hydroxyla .9 13 44 out deleteriously alfecting their anti-soiling character- (c) Test. Hydrazlne .9 16 30 istics a Test. Aniline .4 12 4s (e) Test- Anilinehydrochlonde. .1 15 35 Although the above examples exemphfy certam 21r- Eg g gjg gjg gmg g 2g conium salts, nitrogen containing bases, textile articles (h) Test 1,6-hexamethylene .4 14 as and operating conditions, it is acknowledged and to be (i) Test "fh Z4 14 understood that equivalent zirconium salts, nitrogen con- (i) Test Morpholine 2.2 14 39 taining bases, textile articles and operating conditions are ii? T e s t ii fiiiifiitifi ii fifif 3 also applicable and can be used with the invention.

' turfurylamine. 3 16 30 What iS claimed is:

EWT LZiEII fitiiit tycrsataaae: 3:2 16 3c A p q f r pit l gem1-pcrmanentant1-so1l1ng charactenstlcs to a textile article compnsed of synthet1c fibers comprising:

(l) Contacting the article with an acidic aqueous solution at a pH of from about 1.5 to less than about 7.0,

at a temperature of from about room temperature Example 8 to about the boiling point thereof, containing es- 40 sentially as solutes from about 0.2% to about 20% Scoured samples of nylon knit are treated as described of a water-soluble zirconium salt and from about in Example 1 except the aqueous solutions (liquor to 0.2% to about 20% of a material selected from the goods ratio being 30:1) contain composit1ons as outlined group consisting of organic and inorganic derivain Table VIII. The pH of the solutions and the results tives of ammonia, the percents based on the weight of the artificial soiling tests are indlcated 1n the followof the textile article; and

ing Table VIII. (2) then, drying the textile article thereby to bond the TABLE VIII Percent improvement of Rcflec- Difiertest pH Initial tance ence in sample of refiecreading refiecover solutance after tance control Sample Sclut1oncompos1t1on tion reading soiling reading sample (a) Control 77 33 44 (b) Te Zirconium acetate, 0.44%; hydroxyl amine sulfate, 1.0%; and acetic acid, 3.0%.- 4.1 77 47 30 32 (0) Test Zirconium acetate, 1.1%; hydroxyl amine sulfate, 3.0%; and acetic acid, 3.0% 4 1 78 59 19 57 ((1) Test Zirconium acetate, 1.1%; hydroxyl amine sulfate, 1.0%; and acetic acid, 3.0%- 4. 1 77 61 26 41 (e) Test.. Zirconium acetate, 1.1%; hydroxyl amine sulfate, 1.0%; and acetic acid, 3.0% 4.1 77 27 39 (f) Test Zirconium acetate, 1.1%; hydroxyl amine sulfate, 1.0%; and acetic acid, 3.0% 4. 1 77 49 28 36 EXAMPLE 9 Scoured samples of nylon knit are treated as described in 'Example lexcept the aqueous solutions contain 1.1% of zirconium acetate (percent based on weight of goods),

evaporation residue of the solution, essentially a zirconium reaction product, to the synthetic fibers.

2. The process of claim 1 wherein the synthetic fiber is selected from the group consisting of polyamide fibers,

acetic acid to adjust the pH of the bath to the numbers polyester fibers, and acrylic fibers.

indicated in Table D( and 3% (based on weight of the sample) of a nitrogen containing base as outlined in Table IX. The aqueous solution containing the ammonia does not contain acetic acid. Results of the artificial soiling test are indicated in Table 3. The process of claim 1 wherein the zirconium salt is zirconium'acetate and the ammonium derivative is bydroxylamine sulfate.

4. The process of claim 1 wherein the acidic aqueous solutionis at a temperature within the range of from 1 1 about 175 F. to about the boiling point temperature of the solution Y S. The process of claim 1 wherein the pH of the acidic aqueous solution is Within the range of from about 2 to about 5.

6. The process of claim 1 wherein the acidic aqueous solution contains from about 0.4% to about 8.0% of the zirconium salt and from about 0.2% to about 5.0% of the ammonium derivative, the percents being based on the weight of the textile article.

7. The process of claim 6 wherein the zirconium salt is zirconium acetate and the ammonium derivative is bydroxylamine sulfate.

8. The process described in claim 1 wherein zirconium salt is selected from the group consisting of zirconium acetate, zirconium oxychloride, zirconium sulfate, zirconium acetylacetonate, potassium zirconyl carbonate, zirconium chloride, zirconium fluoride, zirconium nitrite, ammonium zirconyl carbonate, sodium zirconyl oxychloride, sodium zirconium glycerinate, and zirconium tetrachloride; and said derivative of ammonia is selected from the group consisting of primary amines, secondary amines, tertiary amines, and quarternary ammonium salts.

9. The process of claim 8 wherein the synthetic fibers are selected from the group consisting of polyamide fibers, polyester fibers, and acrylic fibers.

10. The process of claim 8 wherein the acidic aqueous solution is at a temperature within the range of from about 175 F. to about the boiling point temperature of the solution.

11. The process of claim 8 wherein the pH of the acidic aqueous solution is within the range of from about 2 to about 5. r

12. The process of claim 8 wherein the acidic aqueous solution contains from 0.4% to about 8.0% of the zirconium-containing material and from about 0.2% to about 5.0% of the ammonium derivative, the percents being based on the weight of the fibers.

13. A process for imparting semi-permanent anti-soiling characteristics to a textile article comprised of synthetic fibers comprising:

(1) Contacting the article with an acidic aqueous solution at a pH of from about 1.5 to less than about 7.0, at a temperature of from about room temperature to about the boiling point thereof, containing essentially as a solute from about 0.2% to about 20% of a water-soluble zirconium salt, the percentage based on the weight of the textile article;

(2) further contacting the article with from about 0.2% to about 20% of a material selected from the group consisting of organic and inorganic derivatives of ammonia, the percent being based on the weight of the textile article, and

12 (3) then drying the textile article thereby to bond the evaporation residue of the solution, essentially a zirconium reaction product, to the synthetic fibers.

14. A textile article comprised of synthetic fibers having bonded and embedded within the surface of said fibers, a microscopic uniform film of particles consisting essentially of the reaction product of a zirconium salt and a derivative of ammonia, said textile article having been produced by the process of (1) immersing the article in an acidic aqueous solution at a pH of from about 1.5 to less than about 7, at a temperature of from about room temperature to about the boiling point thereof, containing essentially as a solute about 02-20 percent of zirconium acetate and about 02-20 percent of a material selected from the group consisting of organic and inorganic derivatives of ammonia, the percents being based on the weight of the textile article; (2) then drying the article.

15. The textile article of claim 14. wherein the synthetic fiber is acrylic fiber.

16. The textile article of claim 14 wherein the synthetic fiber is a polyamide fiber. v v

17. A textile article comprised of synthetic fibers having bonded and embedded within the surface of said fibers a uniform microscopic uniform film of particles consisting essentially of a zirconium reaction product which is the residue of an evaporated acidic aqueous solution of from about 0.2% to about 20% of a water-soluble zirconium salt and from about 0.2% of a material selected from the group consisting of organic and inorganic derivatives of ammonia, the percents being based on the weight of the textile article.

References Cited UNITED STATES PATENTS 2,361,830 10/ 1944 Edelstein 1l792 3,041,199 6/1962 Miller et a1 117-62 3,058,850 10/ 1962 Sell 117-76 3,450,555 '6/ 1969 Bridgeford 11762 3,429,647 2/ 1969 Yao et al. 8-21 OTHER REFERENCES v Blumenthal: Zirconium Chemicals Their Application to Textiles, Rayon and Synthetic Textiles, pp. 81-83, December 1950.

WILLIAM D. MARTIN, Primary Examiner R. H'USACK, Assistant Examiner US. Cl. X.-R.

1l7138.8 N, F, VA, E, D, 139.5 CQ, OF, 169; 252 8.6 

